Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2016 Feb 1;7(2):932-938.
doi: 10.1039/c5sc03780h. Epub 2015 Oct 20.

Chirality sensing of tertiary alcohols by a novel strong hydrogen-bonding donor - selenourea

Guangling Bian  1 , Shiwei Yang  1 , Huayin Huang  1 , Hua Zong  1 , Ling Song  1 , Hongjun Fan  2 , Xiaoqiang Sun  3
Affiliations

Chirality sensing of tertiary alcohols by a novel strong hydrogen-bonding donor - selenourea

Guangling Bian et al. Chem Sci. .

Abstract

Chemical sensors are powerful for the fast recognition of chiral compounds. However, the established sensing systems are less effective for chiral tertiary alcohols. The chiral tertiary alcohol group is an important structural unit in natural products and drug molecules, and its enantioselective recognition represents a significant and challenging task. In this paper, a novel type of chiral bisselenourea sensor was first synthesized and used as a strong hydrogen-bonding donor for highly efficient chiral recognition of a diverse range of tertiary alcohols. The obtained sharply split NMR signals are well-distinguishable with a large (up to 0.415 ppm) chemical shift nonequivalence. The NMR signal of the hydroxyl hydrogen atom was first employed for enantiomeric excess determination of tertiary alcohols, giving accurate results with <2% absolute errors. The 2D NOESY spectra and computational studies suggest that the geometrical differentiation of the formed diastereomeric complexes between the sensor and tertiary alcohols enables the chiral discrimination of the hydroxyl hydrogen signals of the tertiary alcohol in the 1H NMR spectrum.

PubMed Disclaimer

Figures

Fig. 1
Fig. 1. Structures of bisthiourea and bisselenourea.
Scheme 1
Scheme 1. Synthesis of bisselenourea (S,S)-CSA-2.
Fig. 2
Fig. 2. Selected regions of the 1H NMR spectra of nonracemic guest F (various ee values) with (S,S)-CSA-2 and the linear correlation between the ee values determined by HPLC and NMR (ee values are defined in terms of (S)-F).
Fig. 3
Fig. 3. A portion of the 500 MHz 2D NOESY spectrum of a solution of racemic guest A (100 mM)/(S,S)-CSA-2 (100 mM) in C6D6 at 25 °C (intermolecular correlations of guest A to (S,S)-CSA-2 are circled in red).
Fig. 4
Fig. 4. Space-filling representations of the complexes.
See this image and copyright information in PMC

References

    1. Huang Z., Yu S., Wen K., Yu X., Pu L. Chem. Sci. 2014;5:3457–3462.
    2. Metola P., Anslyn E. V., James T. D., Bull S. D. Chem. Sci. 2012;3:156–161.
    3. Miyabe T., Iida H., Ohnishi A., Yashima E. Chem. Sci. 2012;3:863–867.
    4. Wei W., Qu K., Ren J., Qu X. Chem. Sci. 2011;2:2050–2056.
    1. Zhang X., Yin J., Yoon J. Chem. Rev. 2014;114:4918–4959. - PubMed
    2. Pu L. Acc. Chem. Res. 2012;45:150–163. - PubMed
    3. Hembury G. A., Borovkov V. V., Inoue Y. Chem. Rev. 2008;108:1–73. - PubMed
    1. Jo H. H., Lin C.-Y., Anslyn E. V. Acc. Chem. Res. 2014;47:2212–2221. - PubMed
    2. Wolf C., Bentley K. W. Chem. Soc. Rev. 2013;42:5408–5424. - PubMed
    1. Mei X., Wolf C. J. Am. Chem. Soc. 2006;128:13326–13327. - PubMed
    2. Zhang P., Wolf C. Chem. Commun. 2013;49:7010–7012. - PubMed
    1. Wen K., Yu S., Huang Z., Chen L., Xiao M., Yu X., Pu L. J. Am. Chem. Soc. 2015;137:4517–4524. - PubMed
    2. Wang C., Wu E., Wu X., Xu X., Zhang G., Pu L. J. Am. Chem. Soc. 2015;137:3747–3750. - PubMed
    3. Feagin T. A., Olsen D. P. V., Headman Z. C., Heemstra J. M. J. Am. Chem. Soc. 2015;137:4198–4206. - PubMed
    4. Bentley K. W., Wolf C. J. Am. Chem. Soc. 2013;135:12200–12203. - PubMed

LinkOut - more resources